Detergent compositions



United States Patent O" DETERGENT COMPOSITIONS Stephen Cajetan Klisch, Belleville, N. J., assignor to Colgate-Palmolive Company, Jersey City, N. 1., a corporation of Delaware N Drawing. Application December 17, 1952 Serial No. 326,597

7 Claims. (Cl. 252-152) The present invention relates to a detergent composition comprising a water-soluble non-ionic aliphatic polyalkylene oxide detergent and a higher fatty acid dialkylolamide, as hereinafter described and claimed.

The non-ionic detergents represent a relatively new development in the detergent field. Such materials possess certain advantages over the ionic detergents by virtue of their non-ionic or weakly polar characteristics. In general, however, such non-ionic detergents have comparatively poor foaming power, and it would beof advantage to control the surface-active characteristics of such agents in order to yield improved foaming power or other desired characteristics. physico-chemical phenomena or mechanisms involved in the action of the detergent composition, such as interfacial tension, critical micellar structure, solubilization, etc., the formulation of detergent compositions in any desired direction is a complex problem.

It has now been discovered that the incorporation of higher fatty acyl dialkylolamides in detergent compositions consisting essentially of water-soluble non-ionic aliphatic detergents are effective to enhance the action of the detergent composition. As an embodiment, the present invention relates to a detergent composition consisting essentially of water-soluble non-ionic aliphatic polyalkyl-' such as up to about carbon atoms and usually from about 2 to about,3 carbon atoms.

arriide having two N-lower alkylol groups of 2 to 3 carbon atoms each, such as RCO-N(CH CH OH) wherein RCO- is essentially lauroyl or the equivalent derived from coconut oil fatty acids or the like. The hydroxyalkyl groups in the dialkylolamides may be monoor poly-hydroxyalkyl. Examples of suitable additives are N,N bis (Z-hydroxyethyl) lanramide; N,N bis (2-hydroxyethyl) myristamide; N,N bis (2-hydroxyethyl) coconut fatty acid amide; N,N bis (2,3-dihydroxypropyl).

lauramide'; N,N bis (2,3-dihydroxypropyl) myristamide; N,N bis (3-hydroxypropyl) lanramide; N,N bis (3-hydroxypropyl) capramide; N,N bis (2-hydroxypropyl) lauramide, N,N bis (2-hydroxypropyl) myristamide; N,N bis (4-hydroxybutyl) lanramide; etc.

i The higher acyl groups may be derived from pure, impure or commercial grades of higher fatty acids and the like.. More particularly, these acids may be produced from fatty oils, fats, greases, and other natural sources In view of the many v Because ofthe excel-; lent results obtained, it is preferred to use the lauroyl;

2,831,815 Patented Apr, 22,, 1958 desired results. Thus, the higher fatty acid dialkylolamide may be derived from coconut oil fatty acids, or commercially pure fatty acids such as a mixture of lauric acid, 9% myn'stic acid, 1% unsaturated acids with a trace of capric acid.

The essential synthetic detergent component is a watersoluble non-ionic aliphatic'detergent. In general, these detergents are the products produced by the introduction of a controlled number of hydrophilic groups, such as ether or hydroxyl groups, into an aliphatic hydrophobiccompound or group. The degree or proportion of hydrophilic groups will vary with the-specific hydrophobic group, but in general will be sufficient to confer the.

desired water-solubility and detersive properties. Thesedetergents are known in the art and the determination of a specific hydrophyilic:hydrophobic relationship for each type is not the essential novelty of the present invention. Such detergents are generally the water-soluble non-ionic polyalkylene oxide condensates with a hydrophobic aliphatic group, the latter containing usuallyat least about 8 carbons, and preferably 8 to 30 carbons.

It is preferred to use the polyoxyethylene' condensates derived from ethylene oxide although other lower alkylene oxides, such as propylene oxide, butyleneoxide and the like have generally similar properties andmay be substituted therefor. While the number of alkylene oxide groups is controlled so as to yield the desired watersolubility and detersive properties and is dependent upon the character of the hydrophobic group, the product in the types of detergents included in the present invention will possess at least about 5 and usually from about 5-50 alkylene oxide groups.

Further suitable detergents are the polyoxyalkylene esters of organic acids,-such as the higher fatty acids,

rosin acids, tall oil, or acids from the oxidation of petro-' leum,,1 etc.

from about 12 to about 30 moles of ethylene oxide or its The polyglycol esters will usually contain equivalent and about 8 to 22 carbons in the acyl group.

Suitable products are refined tall oil condensed with 16',

or 20 ethylene oxide groups, or similar polyglycol esters of lauric, stearic, oleic acids, etc.

Additional non-ionic agents are the polyalkylene oxide condensates with higher fatty acid amides, such as the.

higher fattyfacid primary amides, monoand .di-ethanolamides. Suitable agents are coconut fatty acid amide condensed with about 10 to 50 moles of ethylene oxide.

The fatty acyl group will similarly have about Ste 22 carbons, and usually about 10 to 18 carbon atoms in such products. The corresponding sulfonamides may also be used if desired.

Other suitable polyether non-ionic detergents are the polyalkylene oxide ethers of higher aliphatic alcohols.

Suitable fatty alcohols having a hydrophobic character, and preferably 8' to 22 carbons, are lauryl, myristyl, cetyl, stearyl and oleyl alcohols which may be condensed with an appropriate amount of ethylene oxide, such as at least about 6, and preferably about 10-60 moles. A typical product is oleyl alcohol condensed with about 12, 15 or 20 moles of ethylene oxide. The corresponding higher alkyl mercaptans or thioalcohols condensed with ethylene oxide are suitable in the present invention also.

The water-soluble polyoxyethylene condensates with polyoxypropylene' glycol s" may be employed in the present invention also. The polypropylene glycol represents the hydrophobic portion of the molecule, exhibiting sufficient Water-insolubility per set at a molecular weight of at least about 900, such as about 900 to 2:400; and preferably about 1200 to 1800. The increasing addition or con densation of ethylene oxide on a given water-insoluble polypropylene glycol tends to increase its watersolubility and raise the melting point such that the products may be water-soluble, and normally liquid, pasty or solid in physical form. The quantity of ethylene oxide varies with the molecular weight of the hydrophobic unit but will usually be at least about and preferably at least about 40% by weight of the product. With an ethylene oxide content of about 40 up to there is usually obtained normally liquid products, above 50% soft wax-like products, and from about 70-90% normally solid products may be obtained which can be prepared in flake form if desired. These condensates may be designated by the following structure:

wherein (C H O) is a polypropylene glycol residue of sufficient number of moles or molecular weight (b) to render the same water-insoluble or hydrophobic, and (a)+(c) represent the number of moles of ethylene oxide condensed therewith to render the product watersoluble.

It is preferred to use such products having a total molecular Weight within the range of about 2,000 to 10,000, and preferably about 4,000 to 8,000. A suitable material is a condensate having a typical average molecular weight of about 7500, the hydrophobic polypropylene glycol being condensed with sufiicient ethylene oxide until' a normally solid watensbluble product is obtained which has an ethylene oxide content of about 80-90% and a melting point usually of about 51-54 C. Another material is a liquid condensate having an ethylene oxide content of 40-50% and a molecular weight of about 4500.

The amount or proportion of dialkylolamide should be sufiicient to act as an organic builder for said polyalkylene oxide condensate or the like. The desired effects in foaming power, washing capacity or the like may be obtained with varying ratios of these essential ingredients, depending upon the specific materials employed, conditions of use, etc. In general, the desired effects may be obtained by selection of proportions of nonionic condensate to dialkylolamide' compound within the range of about 100:1 to about 1:4, usually about 50:1 to about 1:2 and preferably between about 20:1 to 1:1 by weight.

The dialkylolamides may be admixed with the nonionic detergents in any suitable manner and at any point during the manufacturing process at which subsequent operations will not adversely modify the properties of the detergent compositions. The compositions may be prepared in the form of solutions, pastes, or in solid particulate form, such as granules or powders.

It is a preferred embodiment that the normally liquid non-ionic compounds and the dialkylolamides be prepared in the form of liquid solutions which are particularly desirable as dish-washing detergent compositions. In such solutions, it is usually desirable that the two essential ingredients be incorporated in a suitable solvent medium, such as water, ethanol and isopropanol (including mixtures thereof). Other suitable lower aliphatic alcohols may be employed if desired. The total concentration of the mixture of non-ionic and dialkylolamide in solution should usually be sutlicient to produce a concentrated solution, such as about 30-90% by weight. More dilute compositions may be employed as shampoos, etc.

Other adjuvant materials may be employed also. The detergent compositions of the present invention may include any of these substances employed by the art in admixture with detergent compositions generally, provided the use of any such materials does not neutralize or remove the desired effects. These adjuvant builders, additires or like materials may be inorganic or organic in structure and may be mixed with the essential ingredients in any suitable manner. Such inorganic Watersoluble builders as the various alkali metal phosphates, particularly the mclecularly-dehydrated polyphosphate salts may be employed in suitable manner. Examples of phosphate builders are pentasodium triphosphate, hexasodium h'e'xametaphosphate, tetrasodium pyrophosphate, etc. Other water-soluble inorganic salts are sodium silicate, sulfate, carbonate, etc. Suitable organic materials such as sodium carboxymethylcellulose or other suitable organic additives may also be employed as desired.

The activation of foaming power by this combination of essential ingredients may be illustrated by pour foam tests. The pour foam test is designed for comparative study of the relative foaming power of liquids and is described in U. S. Patent No. 2,315,983 to Ross and Miles. In such test, a portion of the solution tobe tested is placed in a jacketed measuring cylinder. The foam is formed by allowing a second portion of solution to stream in from a fixed height through a standard orifice, resulting in a particular foam height generated by each test solution. The foam height in millimeters of solutions tested in accordance with the Ross et al., patent at various time intervals is an indication of the foam volume and stability.

The desirable effect of the dialkylolamide additive with various non-ionic detergents may be illustrated by the initial foam height results set forth in Table I below, which are obtained using thepour foam test at 0.04% concent'ration of eachdetergent solution in distilled water at- 110 F The dialkylolamide used in these tests is substantially pure lauroyl diethanolamide. Where proportionate amounts of lauroyl diethanolamide are indicated (e. g.- 5%, 20%) such amounts are by weight of the nonionic detergent.

TABLE I Percent Dialkylolamide N oil-Ionic Detergent A=Sterox SE'polyoxyethylene thioether condensate. B=Red oil condensate with about 15 m. ethylene oxide. C=Ooccnut amide condensate with about 50 m. ethylene oxide. D= Coconut amide condensate with about 15 to. ethylene oxide.

E= Pluronics L ls-ethyle he oxide condensate of polypropylene glycol contalnlug about 10-50% ethylene oxide and a M. W. of about 4500. F=Pluronics F6Sethylcne oxide condensate of polypropylene glycol containing about ethylene oxide and a M. W. of about 7000. G=Rollued tall oil acids condensed with about 16-20 m. ethylene oxide.

H=Sorbitan monopalmitate polyoxyethylene condensate.

It has been found that variation in the chain length of the acyl radical of the dialkylolamide has a material effect on the foaming power when these compounds are employed in admixture with the non-ionic detergents. As previously indicated, the dialkylolamide consisting essentially of the lauroyl derivative has a remarkable activating effect onthe foaming power. Other higher fatty acyl derivatives have a variable influence. The capryl, myristoyl and palmitoyl diethanolamide exhibit a moderate beneficial effect on foaming whereas the stearoyl derivative generally has an adverse c feet on the foaming power.

The following formulations are additionally illustrative of the nature of the present invention and it will be under- Example Ill Non-ionic polyethylene oxide condensate detergent 20 Myristoyl diethanolamide 1 Example 1V Non-ionic polyethylene oxide condensate detergenL- Palmitoyl diethanolamide 1 The term consisting essentially of as used in the definition of the ingredients present in the composition claimed is intended to exclude the presence of other materials in such amounts as to interfere substantially with the properties and characteristics possessed by the composition set forth but to permit the presence of other materials in such amounts as not substantially to effect said properties and characteristics adversely.

Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor without departing from the principles and true spirit of the invention.

Having described the invention what is desired to be secured by Letters Patent is:

1. A detergent composition consisting essentially of a water-soluble non-ionic aliphatic polyalkylene oxide detergent selected from the group consisting of (a) watersoluble non-ionic polyalkylene oxide condensates with an aliphatic hydrophobic compound having 8 to carbon atoms, said condensates containing about 5 to 50 alkylene oxide groups of 2 to 4 carbon atoms each and (b) Watersolube non-ionic polyoxyethylene condensates with polyoxypropylene glycol containing about 20 to 90% ethylene oxide and having a molecular weight of about 2,000 to 10,000; and an amide compound having the formula:

wherein RCO- represents a saturated higher fatty acyl group of 10 to 16 carbon atoms, and R and R" are lower hydroxyalkyl groups of up to about 5 carbon atoms each, the ratio of said non-ionic detergent to said amide compound being from about 100:1 to about 1:4 by weight and sufficient to improve the foaming power of said non-ionic detergent.

2. A detergent composition in accordance with claim 1 containing a diethanolamide having the formula:

wherein RCO- is a saturatedfatty acyl radical of 10 to 16 carbon atoms, the ratio of said non-ionic detergent to said fatty acyl diethanolamide being from 50:1 to about 1:2 by weight.

3. A detergent composition in accordance with claim 2 wherein said amide is lauroyl diethanolamide.

4. A detergent composition consisting essentially of water-soluble non-ionic polyoxyethylene ester of higher fatty acids having about 12 to 30 moles of ethylene oxide, and as an organic builder therefor an amide compound having the formula:

wherein RCO is a saturated fatty acyl radical of 10 to 16 carbon atoms, the ratio of said non-ionic compound to amide compound being from about :1 to about 1:4 by weight and sufiicient to improve the foaming power of said non-ionic polyoxyethylene material.

5. A detergent composition consisting essentially of water-soluble non-ionic polyoxyethylene esters of tall oil fatty acids having about 12 to 30 moles of ethylene oxide and as an organic builder therefor an amide compound having the formula:

wherein RCO- is a saturated fatty acyl radical of 10 to 16 carbon atoms, the ratio of said non-ionic compound to amide compound being from about 100:1 to about 1:4 by weight and suificient to improve the foaming power of said non-ionic polyoxyethylene material.

6. A detergent composition consisting essentially of water-soluble non-ionic polyoxyethylene condensate with polyoxypropylene glycol containing about 20 to 90% ethylene oxide and having a molecular weight of about 2,000 to 10,000, and as an organic builder therefor an amide compound having the formula:

to improve the foaming power of said non-ionic condensate.

References Cited in the file of this patent UNITED STATES PATENTS 2,383,737 Richardson Aug. 28, 1945 2,576,913 Baird et a1 Dec. 4, 1951 2,607,740 Vitale et a1. Aug. 29, 1952 OTHER REFERENCES Alrose: Technical Bulletin, by Alrose Chemical Co., Providence, Rhode Island; 1946, 4 pp.

Pluronics (Information on Applications of) by Wyandotte, March 1, 1952.

Hackhs Chemical Dictionary, by Grant, 3rd ed., pp. 164, pub. by Blakiston Co., Phila. (1944). 

1. A DETERGENT COMPOSITION CONSITING ESSENTIALLY OF A WATER-SOLUBLE NON-IONIC ALIPHATIC POLYALKLENE OXIDE DETERGENT SELECTED FROM THE GROUP CONSISTING OF (A) WATERSOLUBLE NON-IONIC POLYALKYLENE OXIDE CONDENSATES WITH AN ALPHATIC HYDROPHOBIC COMPOUND HAVING 8 TO 30 CARBON ATOMS, SAID CONDENSATES CONTAINING ABOUT 5 TO 50 ALKYLENE OXIDE GROUPS OF 2 TO 4 CARBON ATOMS EACH AND (B) WATERSOLUBLE NON-IONIC POLYOXYETHYLENE CONDENSATES WITH POLYOYPROPYLENE CONTAINING ABOUT 20 TO 90% ETHYLENE OXIDE AND HAVING A MOLECULAR WEIGHT OF ABOUT 2,000 TO 10,000; AND AN AMIDE COMPOUND HAVING THE FORMULA: 